3-hydroxy - 4 - sulfone quinophthalone dyestuffs and process for making them

ABSTRACT

3-HYDROXY-QUINOPHTHALONE DYESTUFFS SUBSTITUTED IN THE 4-POSITION BY A SULFONE GROUP, AND A PROCESS FOR PREPARING THEM. SAID DYESTUFFS YIELDS ON SYNTHETIC FIBROUS MATERIALS, ESPECIALLY THOSE FROM POLYETHYLENE TREPHTHALATES, YELLOW DYEINGS HAVING GOOD FASTNESS TO LIGHT, WET PROCESSING AND SOLVENT AND A REMARKABLY GOOD FASTNESS TO THERMOFIXATION AND IRONING.

United States Patent Olfice 3 655 670 S-HYDROXY 4 SUI JFOI WE QUINOPHTHALONE DYESTUFF S AND PROCESS FOR MAKING THEM Ernst Spietschka, Oberaurolf, and Friedrich Ische, Kelkheiru, Taunns, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany No Drawing. Filed May 19, 1969, Ser. No. 825,970 Claims priority, application Germany, May 24, 1968,

P 17 69 436.9 Int. Cl. C07d 33/38 US. Cl. 260-283 S 6 Claims ABSTRACT OF THE DISCLOSURE 3-hydroxy-quinophthalone dyestuffs substituted in the 4-position by a sulfone group, and a process for preparing them. Said dyestuffs yield on synthetic fibrous materials, especially those from polyethylene terephthalates, yellow dyeings having good fastness to light, wet processing and solvents and a remarkably good fastness to thermofixation and ironing.

The present invention provides quinophthalone dyestuffs having the general formula o so a Y Q a m c 6 Zn 4 N 9 a 06 in which R represents an aryl radical, an aliphatic or cycloaliphatic radical or a heterocyclic ring, Y represents hydrogen or halogen, a nitro group or a phenyl radical, Z represents hydrogen or halogen, m stands for an integer from 1 to 4 and n is 1 or 2 and a process for preparing same.

In German Auslegeschrift 1,168,862 compounds of the quinophthalone series are disclosed as suitable for dyeing polyester fibres.

From substituted quinophthalones 4-bromo-3-hydroxyquinophthalone, a dye'stutf especially fast to light in regard to polyester fibres and of moderate fastness to thermofixation is described in U.S. Pat. No. 3,036,876 and British patent specification 1,036,389.

It has now been found that new quinophthalone dyestuffs fast to thermofixing and corresponding to the general formula s0 R Y ll o C n I N 9 a o in which R represents an aryl radical, an aliphatic or cycloaliphatic radical or a. heterocyclic ring, Y represents hydrogen or halogen, a nitro group or a phenyl radical, Z represents hydrogen or halogen, m stands for an integer from 1 to 4 and n is l or '2 are obtained by reaction of 4-halogeno 3 hydroxyquinophthalone of the general formula 0 t Ye ii no 3,655,670 Patented Apr. 11, 1972 in which R is defined as above and Me represents the ion of an alkali metal.

The aryl radical R in the above-identified formula preferably is a phenyl, naphthyl, anthraquinonyl or fiuorenyl radical. Said radicals may carry one or more substituents, for example, hydroxy, al-koxy, nitro carboalkoxy, carboxyl, amino, alkyl, phenyl, naphthyl or benzyl groups or halogen atoms. The aliphatic or cycloaliphatic radical R which, preferably, is an alkyl or cycloalkyl radical or the heterocyclic ring R in the afore-said formula may likewise carry substituents, for example hydroxy, alkoxy, aryloxy, especially pheuoxy, cyano, sulfonyl, amino or aryl groups, preferably phenyl or naphthyl groups or halogen atoms.

As suitable starting substances of the quinophthalone series for example 4-bromo-3-hydroxy-quinophthalone, 4-chloro-3-hydroxy-quinophthalone, 4,5,6'-tribrotno-3-hydroxy-quinophthalone, 4,4,5',-6,7-pentabromo-3-hydroxy-quinophthalone, 1 4-bromo-4',7-dichloro-3-hydroxy-quinophthalone, 4-bromo-4',5,6',7-tetrachloro-3-hydroxy-quinophthalone, 4-bromo-4' fiuoro-3-hydroxy-quinophthalone, 4-bromo-5-nitro-3-hydroxy-quinophfihalone, 4,6-dibromo-3-hydroxy-quinophthalone, 4-1bromo-5,7-dichloro-3-hydroxy'quinophthalone and 4-bromo-'5-phenyl-3 -hydroxy-quinophthalone may be used.

Suitable salts of sulfinic acids are, for example, sodium or potassium salts of methane-sulfinic acid,

ethanesulfinic acid,

pentane-l-sulfinic acid, octane-l-sulfinic acid, dodecane-l-sulfinic acid, chloromethane sulfinic acid, ocetane-l-sulfinic acid, dodecane-l-sulfinic acid, chloro-methane-sulfinic acid, Z-hydroxy-ethane-l-sulfinic acid, aminomethane-sulfinic acid, benzene-sulfinic acid, 4-toluene-sulfinic acid, 3,4-dimethyl-benzene-sulfinic acid, 2,4,5-trimethyl-benzene-sulfinic acid, 4-nitrobenzene-sulfinic acid, 2,4-dinitrobeuzene-sulfinicacid, 4-chlorobenzene-sulfinic acid, 4-fluorobenzene-sulfinic acid, 4-iodobenzene-suliinic acid, 2-chloro-5-nitrobenzene-sulfinic acid, 1 4-hydroxy-3-carboxy-benzene-sulfinic acid, 3,S-dicarboxy-benzene-sulfinic acid, 4-amino-toluene-2-sulfinic acid, 1-methoxy-i2-acetylamino-benzene-4-sulfinic acid, 2-methoxy-benzene-sulfinic acid, 4-methoxy-benzene-sulfinic acid, 4-n-dodecylbenzene-sulfinic acid, cyclohexane-sulfinic acid, naphthalene-l-sulfinic acid, anthraquinone-l-sulfinic acid, fluorene-l-sulfinic acid and benzthiazol-Z-sulfinic acid.

Such sulfinic acids are disclosed, for example, in Ullmans Encyklopadie der Technischen Chemie, (1965), vol. 16,

3 pp. 486490, and Houben-Weyl, Methoden der Organischen Chemie, (1955), vol. '9, pp. 289-296.

The reaction is preferably conducted in a polar solvent which has a good dissolving power for alkali metal salts were obtained melting at 280 C. It dyed polyethyleneterephthalate fibres and films yellow shades very fast to light, wet processing and thermofixing.

of sulfinic acids. As such solvents for example phosphoric 5 EXAMPLE 2 acid-tris-dimethylamide, dimethylfomnamide, N methylacetamide, dimethyl-sulfoxide and the like are convenient. Parts 9 9 l 6 In general, the reaction compounds are employed in the Parts i sodium salt of b.enzene'sulfimc .acld were amounts calculated. In some cases the alkali metal salt of duced Into 100 Parts ofodlmethylformimlde and the p" suifinic acid is advantageously used in a slighter excess, 10 ture was heated to f 1500 no more Startmg for example about substance was ascertained. The whole was cooled to room The temperature at which the reaction proceeds detemperature and muted with 9 parts of f The pends on the reaction components and the type of solvent dyestuff drawn Washed with Water and dned' used. In general, it is advantageously, in the range be- 11 Parts 95% of the thaory of the dyestuff of tween 80 and 180 C., preferably between about 100 15 mula and 150 C.

The dyestuif is isolated by cooling of the solution and suction-filtration of the crystallized dyestuif or by pouring so,@ the solution in water or a lower alcohol, for example methanol and drawing 01f the precipitated dyestuif. d H0 The dyestuffs of the invention yield on synthetic fibrous materials, especially those consisting of polyethylenei G g terephthalates, yellow dyeings having a good fastness to H light, wet processing and solvents and remarkably good 0 fastness to thermofixation and ironing. The dyeings pro- 9 duced with the dyestuffs of the invention show in comparison to dyeings obtained with 3-hydroxy-quinophthalone or 4-bromo-3-hydroxy-quinophthalone a superior fastness to thermofixation. were obtained melting at 287 C.

In order to produce fast dyeings, polyester materials It dyed polyethylene terephthalate fibres and films yelare treated with the said dyestuffs in the presence of carlow shades having very good fastness properties, in parriers at between 80 and 110 C. or, without carriers, at ticular excellent fastness to thermofixation. between 110 and 140 C. In order to produce prints, aqueous printing pastes are printed on the polyester tissue EXAMPLE 3 which is, subsequently, steamed in the presence of a car- I rier at between 95 and 110 C. or, in the absence there- 9 Parts of Y Y'q p and 6 f at between 20 and The dyeing or printing parts of potassium salt of 3 chloro toluene 6 sulfinic can likewise be effected by the so-called thermosol process acid were {ntroduced Into 100 Parts of dimethyl-slllfoxide wherein the padded or printed materials are shortly suband the mlXtUIe heated to to untll in a jected to a heat treatment at between 180 and 200 C. 40 Sample no more startlng material s ra d- The bat The dyestuifs provided by the instant process may be used was cooled to room temperature and diluted With 500 with as good result also for dyeing polyethylene terephl of methanol- The dyeshlfi Was drawn washed thalates in the mass. with methanol and water and dried.

The following examples illustrate the invention but they 10 Parts 76% of the theory of the dyestuff coffeare not intended to limit it thereto. The parts and perspohdmg t0 the formula centages are by weight unless otherwise stated.

EXAMPLE 1 a 10 parts of 4-bromo-3-hydroxy-quinophthalone and 5 parts of sodium salt of methane-sulfinic acid were introo Cl duced into 100 parts of phosphoric acid-tris-dimethylll amide and the mixture was heated to 100 C. until no 0 HO more starting substance was ascertained subsequently the mixture was cooled to room temperature and introduced 0 fQ into 500 parts of methanol. The dyestuff was drawn oif, H washed with methanol and water and dried. 9 parts 0 i.e. 94% of the theory of the dyestufi of formula sot-0H3 l: I

Ho were obtained melting at 250 C.

0 GB Said dyestuif dyed polyethylene-terephthalate fibers and N films yellow shades very fast to light, wet processing and H thermofixation.

b In the following table further dyestuifs are listed obtamable by the method disclosed in Examples 1 to 3.

Starting substance Reactcd with- Dyestufi sh d 4-bromo-3-hydroxy Sodium salt ofquinophthalone Ethane-suifinic acid 4-0thylsulfonyl-3-hydroxy-quinophthalone D Phenthane-(1)-sulfinic acid 4-n-pentylsullonyl-3-hydroxy-quinophtha1onc 4-n-oetylsulfonyl-3-hydroxy-quinophthalone 4-chloromethy1sulfonyl-3-hydroxy-qu.inophtha1one.

z-hydroxyethane-sulfinie acid 4-B-l 1ydroxy-ethylsuifonyl-3-hydroxy-quinophthalone Do. 4-toluene-su1finic acid 4-(4 -r1cthyl-phenyl-sulionyl)-3-hydroxy-qulnophtha1one D0. 3,4-dimcthyi-benzene-suifime acid. 4-(3 1 -dimethyi-pheny1-su1fonyi)-3-hydroxy-qumophthaione Do. 2-rncthoxy-bcnzene-sulfimc acid. 4-(2 -methoxy-phenyl-sulfonyl) -3-hydroxy-qu1nophthalone Do. 4-mtro-benzene-su1finic acid 4-(4 -nitro-phenyi suliony1) -3-hydroxy-quinophthalone Do. 4-chloro-benzene-suifinic acid. 4-(4 chloro-phenyl-sulfonyl)-3-hydroxy-quinophthalone Do. 4-fluoro-benzene-sulfinic acid 4-(4 -iiuoro-phenyl-su1fonyi)-3-hydroxy-quinophthalonc Do. 

